EP2291445A1 - Procédés pour maîtriser l'encrassement et améliorer des compositions - Google Patents

Procédés pour maîtriser l'encrassement et améliorer des compositions

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Publication number
EP2291445A1
EP2291445A1 EP20090767465 EP09767465A EP2291445A1 EP 2291445 A1 EP2291445 A1 EP 2291445A1 EP 20090767465 EP20090767465 EP 20090767465 EP 09767465 A EP09767465 A EP 09767465A EP 2291445 A1 EP2291445 A1 EP 2291445A1
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European Patent Office
Prior art keywords
metal
ethylene
percent
polymer
peak
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Granted
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German (de)
English (en)
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EP2291445B1 (fr
Inventor
Anthony J. Castelluccio
Jeffrey J. Dean
Alec Y. Wang
Lindsey Anne Miller
Pradeep Jain
Roger L. Kuhlman
Angela N. Taha
Larry Shayne Green
Gary R. Marchand
Sean W. Ewart
Jeffrey A. Sims
Chris Blaschke
Brandon Fails
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/08—Low density, i.e. < 0.91 g/cm3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/11—Melt tension or melt strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/19—Shear ratio or shear ratio index
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/20—Activation energy or enthalpy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • This invention relates to improved processes employing a post-reactor heat exchanger.
  • the invention relates to (1) reaction processes resulting in less heat exchanger fouling and (2) compositions with improved characteristics, e.g., color.
  • ⁇ T > 48°C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O 0 C; or
  • (6) a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ - olefin interpolymer; or
  • the ethylene/ ⁇ -olefin multiblock interpolymer characteristics ( 1) through (7) above are given with respect to the ethylene/ ⁇ -olefin interpolymer before any significant crosslinking, i.e., before crosslinking.
  • the ethylene/ ⁇ -olefin interpolymers useful in the present invention may or may not be crosslinked depending upon the desired properties.
  • characteristics (1) through (7) as measured before crosslinking is not meant to suggest that the interpolymer is required or not required to be crosslinked - only that the characteristic is measured with respect to the interpolymer without significant crosslinking.
  • Crosslinking may or may not change each of these properties depending upon the specific polymer and degree of crosslinking.
  • Figure 2 shows plots of delta DSC-CRYSTAF as a function of DSC Melt
  • Figure 3 shows the effect of density on elastic recovery for unoriented films made from inventive interpolymers(represented by the squares and circles) and traditional copolymers (represented by the triangles which are various Dow AFFINITY ® polymers).
  • inventive interpolymers represented by the squares and circles
  • traditional copolymers represented by the triangles which are various Dow AFFINITY ® polymers.
  • the squares represent inventive ethylene/butene copolymers; and the circles represent inventive ethylene/octene copolymers.
  • Figure 5 is a plot of octene content of TREF fractionated ethylene/ 1-octene copolymer fractions versus TREF elution temperature of the fraction for the polymer of Example 5 (curve 1) and for comparative F (curve 2).
  • the squares represent Example F*; and the triangles represent Example 5.
  • Figure 6 is a graph of the log of storage modulus as a function of temperature for comparative ethylene/ 1-octene copolymer (curve 2) and propylene/ ethylene- copolymer (curve 3) and for two ethylene/ 1-octene block copolymers of the invention made with differing quantities of chain shuttling agent (curves 1).
  • Figure 7 shows a plot of TMA (l mm) versus flex modulus for some inventive polymers (represented by the diamonds), as compared to some known polymers.
  • the triangles represent various Dow VERSIFY ® polymers; the circles represent various random ethyl ene/styrene copolymers; and the squares represent various Dow AFFINITY ® polymers.
  • Polymer means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “'interpolymer.”
  • ethylene/ ⁇ -olefln block interpolymer or "ethylene/ ⁇ -olefin multiblock interpolymer”generally refer to block copolymers comprising ethylene and an a - olefin having 3 or more carbon atoms.
  • ethylene comprises the majority mole fraction of the whole polymer, i.e., ethylene comprises at least about 50 mole percent of the whole polymer. More preferably ethylene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial remainder of the whole polymer comprising at least one other comonomer that is preferably an ⁇ -olefin having 3 or more carbon atoms.
  • the preferred composition comprises an ethylene content greater than about 80 mole percent of the whole polymer and an octene content of from about 10 to about 15, preferably from about 15 to about 20 mole percent of the whole polymer.
  • the ethylene/ ⁇ -olefin block interpolymers do not include those produced in low yields or in a minor amount or as a byproduct of a chemical process. While the ethylene/ ⁇ -olefin block interpolymers can be blended with one or more polymers, the as-produced ethylene/ ⁇ -olefin block interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
  • Such ethylene/ ⁇ -olefin block interpolymers are described in, for example, U.S. Patent Application Publication No. US 2006/0199930 Al published on September 7, 2006 and incorporated herein by reference.
  • composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the ingredients or materials of the composition.
  • compositions of the present invention include grafted or coupled compositions wherein an initiator or coupling agent reacts with at least a portion of one or more polymers and/or at least a portion of one or more fillers.
  • Melt flow rate determinations can also be performed with even higher weights, such as in accordance with ASTM D- 1238 Condition 190 °C/21.6 kg, and is known as I 2 ,.
  • Melt Flow Rate Ratio is the ratio of melt flow rate (Iio) to melt flow rate (I 2 ) unless otherwise specified.
  • the ethylene/ ⁇ -olefin interpolymers comprise ethylene and one or more copolymerizable ⁇ -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/ ⁇ -olefin interpolymers are block interpolymers, preferably multi-block interpolymers or copolymers.
  • the terms "interpolymer” and copolymer” are used interchangeably herein.
  • the multi-block copolymer can be represented by the following formula:
  • n is at least 1 , preferably an integer greater than 1 , such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, "A” represents a hard block or segment and "'B” represents a soft block or segment.
  • As and Bs are linked in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped fashion.
  • a blocks and B blocks are randomly distributed along the polymer chain.
  • the block copolymers usually do not have a structure as follows.
  • the block copolymers do not usually have a third type of block, which comprises different comonomer(s).
  • each of block A and block B has monomers or comonomers substantially randomly distributed within the block.
  • neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
  • the multi-block polymers typically comprise various amounts of "hard” and
  • “soft” segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer.
  • the comonomer content (content of monomers other than ethylene) in the hard segments is less than about 5 weight percent, and preferably less than about 2 weight percent based on the weight of the polymer.
  • the hard segments comprises all or substantially all ethylene.
  • Soft segments refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than about 5 weight percent, preferably greater than about 8 weight percent, greater than about 10 weight percent, or greater than about 15 weight percent based on the weight of the polymer.
  • the comonomer content in the soft segments can be greater than about 20 weight percent, greater than about 25 weight percent, greater than about 30 weight percent, greater than about 35 weight percent, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 weight percent.
  • the soft segments can often be present in a block interpolymer from about 1 weight percent to about 99 weight percent of the total weight of the block interpolymer, preferably from about 5 weight percent to about 95 weight percent, from about 10 weight percent to about 90 weight percent, from about 15 weight percent to about 85 weight percent, from about 20 weight percent to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, from about 40 weight percent to about 60 weight percent, or from about 45 weight percent to about 55 weight percent of the total weight of the block interpolymer.
  • the hard segments can be present in similar ranges.
  • the soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR.
  • Such methods and calculations are disclosed in a concurrently filed U.S. Patent Application Serial No. 1 1/376,835, Attorney Docket No. 385063-999558, entitled "Ethylene/ ⁇ -Olef ⁇ n Block lnterpolymers", filed on March 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated by reference herein in its entirety.
  • crystalline refers to a polymer that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique.
  • Tm first order transition or crystalline melting point
  • amorphous refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.
  • multi-block copolymer or “segmented copolymer” refers to a polymer comprising two or more chemically distinct regions or segments (referred to as “blocks”) preferably joined in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion.
  • the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property.
  • the multi-block copolymers are characterized by unique distributions of both polydispersity index (PDI or Mw/Mn), block length distribution, and/or block number distribution due to the unique process making of the copolymers.
  • the polymers when produced in a continuous process, desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2. and most preferably from 1.8 to 2.1.
  • the polymers When produced in a batch or semi-batch process, the polymers possess PDl from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
  • R R L +k*(R u -R L ), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.
  • any numerical range defined by two R numbers as defined in the above is also specifically disclosed.
  • ventive interpolymer (also referred to as “inventive interpolymer” or “inventive polymer”) comprise ethylene and one or more copolymerizable ⁇ -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multi-block copolymer.
  • block interpolymer preferably a multi-block copolymer.
  • the ethylene/ ⁇ -olefin interpolymers are characterized by one or more of the aspects described as follows.
  • the ethylene/ ⁇ -olefin interpolymers used in embodiments of the invention have a M w /M ⁇ from about 1.7 to about 3.5 and at least one melting point, T m , in degrees Celsius and density, d, in grams/cubic centimeter, wherein the numerical values of the variables correspond to the relationship:
  • T m > -2002.9 + 4538.5(d) - 2422.2(d) 2 , and preferably
  • T m > -6288.1 + 13141 (d) - 6720.3(d) 2 , and more preferably
  • T m > 858.91 - 1825.3(d) + 1 1 12.8(d) 2 .
  • the inventive interpolymers exhibit melting points substantially independent of the density, particularly when density is between about 0.87 g/cc to about 0.95 g/cc.
  • the melting point of such polymers are in the range of about 1 10 0 C to about 130 0 C when density ranges from 0.875 g/cc to about 0.945 g/cc.
  • the melting point of such polymers are in the range of about 1 15 0 C to about 125 0 C when density ranges from 0.875 g/cc to about 0.945 g/cc.
  • the ethylene/ ⁇ -olefin interpolymers comprise, in polymerized form, ethylene and one or more ⁇ -olefins and are characterized by a ⁇ T, in degree Celsius, defined as the temperature for the tallest Differential Scanning Calorimetry (“DSC”) peak minus the temperature for the tallest Crystallization Analysis Fractionation (“CRYSTAF”) peak and a heat of fusion in J/g, AH, and AT and AH satisfy the following relationships:
  • ⁇ T is equal to or greater than 48 0 C for ⁇ H greater than 130 J/g.
  • the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C, and ⁇ H is the numerical value of the heat of fusion in J/g. More preferably, the highest CRYSTAF peak contains at least 10 percent of the cumulative polymer.
  • the ethylene/ ⁇ -olefin interpolymers have a molecular fraction which elutes between 40 0 C and 13O 0 C when fractionated using Temperature Rising Elution Fractionation ("TREF"), characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer contains the same comonomer(s), and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the block interpolymer.
  • TEZ Temperature Rising Elution Fractionation
  • the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.
  • the ethylene/ ⁇ -olefin interpolymers are characterized by an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured on a compression-molded film of an ethylene/ ⁇ -olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/ ⁇ -olefin interpolymer is substantially free of a cross-linked phase:
  • Figure 3 shows the effect of density on elastic recovery for unoriented films made from certain inventive interpolymers and traditional random copolymers.
  • inventive interpolymers For the same density, the inventive interpolymers have substantially higher elastic recoveries.
  • the ethylene/ ⁇ -olefin interpolymers have a tensile strength above 10 MPa, preferably a tensile strength > 1 1 MPa, more preferably a tensile strength > 13MPa and/or an elongation at break of at least 600 percent, more preferably at least 700 percent, highly preferably at least 800 percent, and most highly preferably at least 900 percent at a crosshead separation rate of 1 1 cm/minute.
  • the ethylene/ ⁇ -olefin interpolymers have (1) a storage modulus ratio, G'(25°C)/G ⁇ i00°C), of from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 7O 0 C compression set of less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, down to a compression set of 0 percent.
  • the ethylene/ ⁇ -olefin interpolymers have a 7O 0 C compression set of less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent.
  • the 70 0 C compression set of the interpolymers is less than 40 percent, less than 30 percent, less than 20 percent, and may go down to about 0 percent.
  • the ethylene/ ⁇ -olefin interpolymers have a heat of fusion of less than 85 J/g and/or a pellet blocking strength of equal to or less than 100 pounds/foot 2 (4800 Pa), preferably equal to or less than 50 lbs/ft 2 (2400 Pa), especially equal to or less than 5 lbs/ft 2 (240 Pa), and as low as 0 lbs/ft 2 (0 Pa).
  • the ethylene/ ⁇ -olefin interpolymers comprise, in polymerized form, at least 50 mole percent ethylene and have a 7O 0 C compression set of less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably less than 40 to 50 percent and down to close zero percent.
  • the multi-block copolymers possess a PDI fitting a
  • the copolymers are further characterized as having both a polydisperse block distribution and a polydisperse distribution of block sizes and possessing a most probable distribution of block lengths.
  • Preferred multi- block copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, the copolymers include at least 5, 10 or 20 blocks or segments including terminal blocks .
  • Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred.
  • the polymer desirably is first fractionated using TREF into fractions each having an eluted temperature range of 1O 0 C or less. That is, each eluted fraction has a collection temperature window of 10 0 C or less.
  • said block interpolymers have at least one such fraction having a higher molar comonomer content than a corresponding fraction of the comparable interpolymer.
  • the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks (i.e., at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a peak (but not just a molecular fraction) which elutes between 4O 0 C and 130 0 C (but without collecting and/or isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy when expanded using a full width/half maximum (FWHM) area calculation, has an average molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer peak at the same elution
  • FWHM full
  • the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
  • the full width/half maximum (FWHM) calculation is based on the ratio of methyl to methylene response area [CH3/CH 2 ] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined.
  • the FWHM area is defined as the area under the curve between Ti and T 2 , where T] and T 2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
  • a calibration curve for comonomer content is made using random ethylene/ ⁇ -olefin copolymers, plotting comonomer content from NMR versus FWHM area ratio of the TREF peak. For this infra-red method, the calibration curve is generated for the same comonomer type of interest.
  • the comonomer content of TREF peak of the inventive polymer can be determined by referencing this calibration curve using its FWHM methyl : methylene area ratio [CH3/CH7] of the TREF peak.
  • Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy preferred. Using this technique, said blocked interpolymers has higher molar comonomer content than a corresponding comparable interpolymer.
  • NMR nuclear magnetic resonance
  • the block interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in 0 C.
  • Figure 4 graphically depicts an embodiment of the block interpolymers of ethylene and 1 -octene where a plot of the comonomer content versus TREF elution temperature for several comparable ethylene/ 1-octene interpolymers (random copolymers) are fit to a line representing (- 0.2013) T + 20.07 (solid line). The line for the equation (- 0.2013) T + 21.07 is depicted by a dotted line. Also depicted are the comonomer contents for fractions of several block ethylene/ 1-octene interpolymers of the invention (multi-block copolymers).
  • FIG. 5 graphically displays the TREF curve and comonomer contents of polymer fractions for Example 5 and comparative F discussed below.
  • the peak eluting from 40 to 130 0 C, preferably from 60 0 C to 95°C for both polymers is fractionated into three parts, each part eluting over a temperature range of less than 10 0 C.
  • Actual data for Example 5 is represented by triangles.
  • an appropriate calibration curve may be constructed for interpolymers containing different comonomers and a line used as a comparison fitted to the TREF values obtained from comparative interpolymers of the same monomers, preferably random copolymers made using a metallocene or other homogeneous catalyst composition.
  • Inventive interpolymers are characterized by a molar comonomer content greater than the value determined from the calibration curve at the same TREF elution temperature, preferably at least 5 percent greater, more preferably at least 10 percent greater.
  • the inventive polymers can be characterized by one or more additional characteristics.
  • the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40 0 C and 130 0 C, when fractionated using TREF increments, characterized in that said fraction has a molar comonomer content higher, preferably at least 5 percent higher, more preferably at least 10, 15, 20 or 25 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer comprises the same comonomer(s), preferably it is the same com
  • the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer.
  • the above interpolymers are interpolymers of ethylene and at least one ⁇ -olefin, especially those interpolymers having a whole polymer density from about 0.855 to about 0.935 g/cm 3 , and more especially for polymers having more than about 1 mole percent comonomer, the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.1356) T + 13.89, more preferably greater than or equal to the quantity (-0.1356) T+ 14.93, and most preferably greater than or equal to the quantity (-0.2013)T + 21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction being compared, measured in 0 C.
  • the blocked interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 0 C greater than or equal to the quantity (- 0.2013) T + 20.07, more preferably greater than or equal to the quantity (-0.2013) T+ 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction being compared, measured in 0 C.
  • the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 4O 0 C and 130 0 C, when fractionated using TREF increments, characterized in that every fraction having a comonomer content of at least about 6 mole percent, has a melting point greater than about 100 0 C.
  • every fraction has a DSC melting point of about 1 10 0 C or higher. More preferably, said polymer fractions, having at least 1 mole percent comonomer, has a DSC melting point that corresponds to the equation:
  • Tm > (-5.5926)(mole percent comonomer in the fraction) + 135.90.
  • the inventive polymer is an olefin interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction which elutes between 40 0 C and 130°C, when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature greater than or equal to about 76°C, has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation:
  • the inventive block interpolymers have a molecular fraction which elutes between 40 0 C and 130 0 C, when fractionated using TREF increments, characterized in that every fraction that has an ATREF elution temperature between 40 0 C and less than about 76°C, has a melt enthalpy (heat of fusion) as measured by DSC, corresponding to the equation:
  • the comonomer composition of the TREF peak can be measured using an IR4 infra-red detector available from Polymer Char, Valencia, Spain (http://www.polymerchar.com/).
  • the "composition mode" of the detector is equipped with a measurement sensor (CH?) and composition sensor (CH3) that are fixed narrow band infra-red filters in the region of 2800-3000 cm “ '.
  • the measurement sensor detects the methylene (CH 2 ) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH 3 ) groups of the polymer.
  • the mathematical ratio of the composition signal (CH 3 ) divided by the measurement signal (CH 2 ) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene alpha-olefin copolymer standards.
  • the detector when used with an ATREF instrument provides both a concentration (CH 2 ) and composition (CH3) signal response of the eluted polymer during the TREF process.
  • a polymer specific calibration can be created by measuring the area ratio of the CH 3 to CH 2 for polymers with known comonomer content (preferably measured by NMR).
  • the comonomer content of an ATREF peak of a polymer can be estimated by applying a the reference calibration of the ratio of the areas for the individual CH 3 and CH 2 response (i.e. area ratio CH 3 /CH 2 versus comonomer content).
  • FWHM FWHM calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram.
  • the full width/half maximum calculation is based on the ratio of methyl to methylene response area [CH3/CH 2 ] from the ATREF infrared detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined.
  • the FWHM area is defined as the area under the curve between Tl and T2, where Tl and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.
  • the inventive ethylene/ ⁇ -olefin interpolymer is characterized by an average block index, ABI, which is greater than zero and up to about 1.0 and a molecular weight distribution, M w /M n , greater than about 1.3.
  • the average block index, ABI is the weight average of the block index ("BI") for each of the polymer fractions obtained in preparative TREF from 20 0 C and 1 10 0 C, with an increment of 5°C: where BI, is the block index for the ith fraction of the inventive ethylene/ ⁇ -olefin interpolymer obtained in preparative TREF, and w, is the weight percentage of the ith fraction.
  • Tx is the preparative ATREF elution temperature for the ith fraction (preferably expressed in Kelvin)
  • P x is the ethylene mole fraction for the ith fraction, which can be measured by NMR or IR as described above.
  • P AB is the ethylene mole fraction of the whole ethylene/ ⁇ -olefin interpolymer (before fractionation), which also can be measured by NMR or IR.
  • T A and P A are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer).
  • the weight average block index, ABI for the whole polymer can be calculated.
  • ABI is greater than zero but less than about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABI is greater than about 0.3 and up to about 1.0. Preferably, ABI should be in the range of from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9.
  • the density of the inventive polymers can be from 0.80 to 0.99 g/cm 3 and preferably for ethylene containing polymers from 0.85 g/cm 3 to 0.97 g/cm 3 .
  • the density of the ethylene/ ⁇ -olefin polymers ranges from 0.860 to 0.925 g/cm 3 or 0.867 to 0.910 g/cm 3 .
  • Catalyst (Al) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2- isopropylphenyl)( ⁇ -naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10/429,024, filed May 2, 2003, and WO 04/24740.
  • Catalyst (A2) is [N-(2,6-di( 1 -methylethyl)phenyl)amido)(2- methylphenyl)( 1 ,2-phenylene-(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of WO 03/40195, 2003US0204017, USSN 10/429,024, filed May 2, 2003, and WO 04/24740.
  • Catalyst (Cl) is (t-butylamido)dimethyl(3-N-pyrrolyl-l , 2,3,3a Ja- ⁇ -inden- 1 - yl)silanetitanium dimethyl prepared substantially according to the techniques of USP 6,268,444:
  • Catalyst (C3) is (t-butylamido)di(4-methylphenyl)(2-methyl-l,2,3,3a,8a- ⁇ -s- indacen- l-yl)silanetitanium dimethyl prepared substantially according to the teachings of US- A-2003/004286:
  • shuttling agents include diethylzinc, di(i- butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, i- butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum, i- butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n- octylaluminum di(ethyl( l-naphthyl)amide), ethylalum
  • the foregoing process takes the form of a continuous solution process for forming block copolymers, especially multi-block copolymers, preferably linear multi-block copolymers of two or more monomers, more especially ethylene and a C3. 2 0 olefin or cycloolefin, and most especially ethylene and a C 4 . 2 0 ⁇ -olefin, using multiple catalysts that are incapable of interconversion. That is, the catalysts are chemically distinct.
  • the process is ideally suited for polymerization of mixtures of monomers at high monomer conversions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes advantaged compared to chain growth, and multi-block copolymers, especially linear multi- block copolymers are formed in high efficiency.
  • inventive interpolymers may be differentiated from conventional, random copolymers, physical blends of polymers, and block copolymers prepared via sequential monomer addition, fluxional catalysts, anionic or cationic living polymerization techniques.
  • inventive interpolymers compared to a random copolymer of the same monomers and monomer content at equivalent crystallinity or modulus, the inventive interpolymers have better (higher) heat resistance as measured by melting point, higher TMA penetration temperature, higher high- temperature tensile strength, and/or higher high-temperature torsion storage modulus as determined by dynamic mechanical analysis.
  • the inventive interpolymers Compared to a random copolymer containing the same monomers and monomer content, the inventive interpolymers have lower compression set, particularly at elevated temperatures, lower stress relaxation, higher creep resistance, higher tear strength, higher blocking resistance, faster setup due to higher crystallization (solidification) temperature, higher recovery (particularly at elevated temperatures), better abrasion resistance, higher retractive force, and better oil and filler acceptance.
  • inventive interpolymers also exhibit a unique crystallization and branching distribution relationship. That is, the inventive interpolymers have a relatively large difference between the tallest peak temperature measured using CRYSTAF and DSC as a function of heat of fusion, especially as compared to random copolymers containing the same monomers and monomer level or physical blends of polymers, such as a blend of a high density polymer and a lower density copolymer, at equivalent overall density. It is believed that this unique feature of the inventive interpolymers is due to the unique distribution of the comonomer in blocks within the polymer backbone.
  • the inventive interpolymers may comprise alternating blocks of differing comonomer content (including homopolymer blocks).
  • inventive interpolymers may also comprise a distribution in number and/or block size of polymer blocks of differing density or comonomer content, which is a Schultz-Flory type of distribution.
  • inventive interpolymers also have a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus, and morphology.
  • the microcrystalline order of the polymers demonstrates characteristic spherulites and lamellae that are distinguishable from random or block copolymers, even at PDI values that are less than 1.7, or even less than 1.5, down to less than 1.3.
  • inventive interpolymers may be prepared using techniques to influence the degree or level of blockiness. That is the amount of comonomer and length of each polymer block or segment can be altered by controlling the ratio and type of catalysts and shuttling agent as well as the temperature of the polymerization, and other polymerization variables.
  • a surprising benefit of this phenomenon is the discovery that as the degree of blockiness is increased, the optical properties, tear strength, and high temperature recovery properties of the resulting polymer are improved. In particular, haze decreases while clarity, tear strength, and high temperature recovery properties increase as the average number of blocks in the polymer increases.
  • shuttling agents and catalyst combinations having the desired chain transferring ability high rates of shuttling with low levels of chain termination
  • other forms of polymer termination are effectively suppressed. Accordingly, little if any ⁇ -hydride elimination is observed in the polymerization of ethylene/ ⁇ -olefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are highly, or substantially completely, linear, possessing little or no long chain branching.
  • both ends of the resulting multi-block copolymer are preferentially highly crystalline.
  • the ethylene ⁇ -olefin interpolymers used in the embodiments of the invention are preferably interpolymers of ethylene with at least one C3-C20 ⁇ -olefin. Copolymers of ethylene and a C3-C20 ⁇ -olefin are especially preferred.
  • the interpolymers may further comprise C4-C 18 diolefin and/or alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, alkenylbenzenes, etc.
  • Examples of such comonomers include C3-C20 ⁇ -olefins such as propylene, isobutylene, 1 -butene, 1 -hexene, 1-pentene, 4-methyl-l-pentene, 1 -heptene, 1-octene, 1-nonene, 1-decene, and the like.
  • C3-C20 ⁇ -olefins such as propylene, isobutylene, 1 -butene, 1 -hexene, 1-pentene, 4-methyl-l-pentene, 1 -heptene, 1-octene, 1-nonene, 1-decene, and the like.
  • 1- Butene and 1-octene are especially preferred.
  • Suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1 ,4-hexadiene, 1 ,7-octadiene, and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene).
  • olefin monomers include, but are not limited to propylene, isobutylene, 1-butene, 1 -pentene, 1-hexene, 1 -heptene, 1-octene, 1 -nonene, 1-decene, and 1 - dodecene, 1 -tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene, 3-methyl- 1-butene, 3- methyl- 1 -pentene, 4-methyl-l -pentene, 4,6-dimethyl- 1-heptene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C4-C40 dienes, including but not limited to 1,3-butadiene, 1,3
  • the ⁇ -olefin is propylene, 1-butene, 1 - pentene, 1 -hexene, 1-octene or a combination thereof.
  • any hydrocarbon containing a vinyl group potentially may be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.
  • polystyrene polystyrene
  • olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, t-butylstyrene, and the like.
  • interpolymers comprising ethylene and styrene can be prepared by following the teachings herein.
  • copolymers comprising ethylene, styrene and a C3-C20 alpha olefin, optionally comprising a C4-C20 diene, having improved properties can be prepared.
  • Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.
  • suitable non-conjugated dienes include, but are not limited to, straight chain acyclic dienes, such as 1,4-hexadiene, 1 ,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5-methyl- 1 ,4-hexadiene; 3,7-dimethyl-l,6-octadiene; 3,7-dimethyl- 1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1 ,5-cyclododecadiene
  • the particularly preferred dienes are 1 ,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2- norbornene (MNB), and dicyclopentadiene (DCPD).
  • the especially preferred dienes are 5- ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
  • the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95.
  • the elastomeric polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefin content of from 10 to 80 percent, based on the total weight of the polymer.
  • the multi-block elastomeric polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an ⁇ -olefin content of from 10 to 40 percent, based on the total weight of the polymer.
  • the amount of the functional group present in the functional interpolymer can vary.
  • the functional group can typically be present in a copolymer-type functional ized interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent.
  • the functional group will typically be present in a copolymer-type functional ized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent.
  • ⁇ T 48 0 C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30 0 C; or
  • (6) a molecular fraction which elutes between 40 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ - olefin interpolymer; or
  • the ethylene/ ⁇ -olefin multiblock interpolymer preferably comprise at least 50 mole percent ethylene.
  • the foulants may be produced in the following manner when employing, for example, diethyl zinc.
  • the polymer may exit the reactor at a high temperature of about 140 0 C or so and then become heated in, for example, a carbon-steel shell and tube post reactor heater (PRH) to from about 240 to about 250 0 C prior to devolatilization.
  • PRH carbon-steel shell and tube post reactor heater
  • a catalyst kill agent and/or water is added to deactivate any catalyst left in solution.
  • the catalyst kill agent must also deactivate the dipolymeryl zinc to produce a more stable Zn species before it reaches the PRH temperatures.
  • dipolymeryl zinc As with many metal alkyl compounds, is converted to a relatively insoluble zinc metal or zinc oxide compound which subsequently results in fouling and/or discolored polymer product. It is hypothesized that this decomposition may occur through a free radical mechanism.
  • the instant inventors discovered that improvements can be achieved by employing one or more of the following four steps:
  • the alkyl group comprises a polymeric chain with a molecular weight of less than about 50,000 although some metal alkyl may not be reacted which means that the alkyl group may sometimes further comprise alkyl groups of about 2 carbons.
  • the alkyl group comprises from about 2 toabout 10,000 carbon atoms, preferably from about 1000 to about 5000 carbon atoms.
  • a suitable acid such that the resulting soluble metal ester is selected from the group consisting of anti-slip agents, mold release agents, nucleating agents, lubricating agents, and anti-fungal agents.
  • a desired additive to the product may be produced in-situ. Desirable amounts of such agents would vary depending upon the application but would at least include an amount to perform the desired function, e.g., an anti-slipping effective amount, an anti-fungal effective amount, or a nucleating effective amount.
  • the reaction between metal alkyl compound with a suitable acid is conducted under suitable conditions to produce a soluble metal ester.
  • suitable conditions may vary depending upon the specific metal alkyl compound, acid, and other compounds present.
  • the conditions employed may simply be the conditions conventionally used to produce the desired polymer product.
  • the desired product is, for example, an ethylene/ ⁇ -olefin block interpolymer
  • the suitable acid may simply be added to the reactor after the polymerization process or, more preferably, the suitable acid is added to the reactor effluent as it leaves the reactor or shortly thereafter.
  • the interpolymer product is substantially free of metal oxide subsequent to the reaction of metal alkyl compound with an acid. This facilitates maintaining the heat exchange efficiency of the post reactor heat exchanger relatively constant over a longer time than if the acid had not been employed. That is, the efficiency drops less than about 2, preferably less than about I , preferably less than about 0.5% per day.
  • the molar ratio of acid to metal is from about 1 : 1 to about 10: 1 , preferably from about 1.25: 1 to about 5: 1, more preferably from about 1.5: 1 to about 3: 1. It may be desirable to mix the acid with water before reacting it with said metal alkyl compound if, for example, a soluble, complex metal ester is desired.
  • complex metal esters include those having the formula ZrUO(C n Ho n+I CO? ⁇ wherein n is from about 5 to about 20.
  • the acid may be mixed with water in a molar ratio of acid to water of from about 10: 1 to about 0.5: 1 , preferably from about 4: 1 to about 7: 1.
  • the amount of water may be from about 20 to about 30 times the amount of metal on a molar basis and/or the amount of water is from about 16 to about 22 times the amount of acid on a molar basis.
  • the useful specific metal:H2O:acid ratios vary depending on the ingredients and often upon the valency of the metal and ratio of metal to oxygen in the metal oxide. In the case of producing ethylene/ ⁇ -olefin block interpolymers using a zinc shuttling agent such as diethyl zinc it has been found that a particularly useful zinc:H 2 ⁇ :acid ratio is about 1-2:24-26: 1.4-1.6.
  • the ionic surfactant may vary depending upon the reactants and, if present, any catalyst and/or chain shuttling agent, as well as, the reaction conditions.
  • suitable ionic surfactants comprise a polar portion and a non-polar portion.
  • ionic surfactants comprise a fatty acid salt such as those selected from the group consisting of alkali metal fatty acid salts, alkaline earth metal fatty acid salts, and mixtures thereof.
  • a particularly preferable ionic surfactant is a salt of stearic acid such as those selected from the group consisting of zinc stearate, calcium stearate, aluminum stearate, and mixtures thereof.
  • the ionic surfactant may be mixed with an effective amount of a suitable antistatic agent.
  • suitable antistatic agents and amounts vary widely depending upon the other ingredients.
  • One suitable antistatic agent used when producing, for example, ethylene/ ⁇ -olefin block interpolymers is an alkoxylated alkylamine such as ethoxylated alkylamine. It has been found that a suitable amount of ethoxylated alkylamine mixed with a salt of stearic acid may be particularly effective in substantially reducing, hindering, or even eliminating the majority of foulant of the PRH and/or discolorant when producing an ethylene/ ⁇ -olefin block interpolymer product.
  • the amount of ionic surfactant to be added varies depending upon the specific metal, other compounds, and reaction conditions.
  • the molar ratio of ionic surfactant to metal is from about 1 :3 to about 1 : 10, preferably from about 1 :4 to about 1 :6, more preferably about 1:5.
  • the ratio of ionic surfactant to metal may be from about 0.5: 1 to about 10: 1 , more preferably from about 1.5: 1 to about 3: 1, more preferably about 2: 1.
  • the amount of deposits on the post reactor heat exchanger may be decreased by a factor of at least five as compared to when an ionic surfactant is not employed in the reaction process.
  • Suitable antioxidants depend on the reactants and other products but for many polymer products such as ethylene/ ⁇ -olefin block interpolymers suitable antioxidants may often be selected from the group consisting of sterically hindered phenols, sterically hindered phenyl phosphites, and mixtures thereof.
  • the antioxidant may be mixed with other suitable compounds such as color stabilizers such as hindered amines like 1,6-hexanediamine, N, N'-bis(2,2,6,6-tetramethyl-4- piperidinyl)-polymer with 2,4,6-trichloro-l ,3,5-triazine, reaction products with N-butyl-l - butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (such as CHIMASSORB 2020), N(Ci 8 H 37 ) I OH (such as IRGASTAB FS 042), all of which are available from Ciba and mixtures thereof.
  • color stabilizers such as hindered amines like 1,6-hexanediamine, N, N'-bis(2,2,6,6-tetramethyl-4- piperidinyl)-polymer with 2,4,6-trichloro-l ,3,5-triazine, reaction products with N-butyl-l - butan
  • the mixture comprising antioxidant and, if desired, one or more color stabilizers, one or more catalyst deactivators, and/or one or more solvents is added to the desired product under conditions sufficient to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound.
  • This may be accomplished in any convenient manner.
  • said mixture is added to the product of said reaction process while passing said product to a post-reactor heat exchanger at an increased temperature.
  • the increased temperature is usually below the vaporization temperature of the components and varies by the process.
  • the antioxidant may be added at a temperature of from about 120 0 C to about 200 0 C.
  • the contacting may be accomplished by employing one or more streams of antioxidant, color stabilizer, catalyst deactivator, solvent, or any of the aforementioned separately or combined at any convenient temperature and pressure.
  • the relative amount of antioxidant and, if desired, one or more color stabilizers, one or more catalyst deactivators, and/or one or more solvents varies depending upon the process. In general, the amount of antioxidant, if any, varies depending upon the end use and requirements of the final product. Similarly, the amount and type of color stabilizer, if any, may vary depending upon the type of catalyst used. However, for ethylene/ ⁇ -olefin block interpolymer product the antioxidant mixture typically comprises from about 0.2 to about 4.5, preferably from about 0.3 to about 3.5, weight percent antioxidant. When color stabilizer is employed the mixture typically comprises from about 0.2 to about 12. preferably from about 2 to about 1 1, weight percent color stabilizer.
  • the conditions employed include inducing boiling over 50%, preferably more than 95% of the surface area of the equipment, e.g, surface of heat exchanger which may be subject to fouling.
  • compositions of the present invention comprise an ethylene/ ⁇ -olefin multiblock interpolymer and a metal ester.
  • the ethylene/ ⁇ -olefin multiblock interpolymer may be characterized before any crosslinking by one or more of the following characteristics:
  • ⁇ T 48 0 C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O 0 C; or
  • the metal ester varies depending upon the desired characteristics ofthe composition but typically is a substituted or unsubstituted aliphatic metal ester.
  • the metal ester preferably comprises from about 6 to about 30 carbon atoms.
  • the substituted or unsubstituted aliphatic group is dependent upon the type of acid that may be employed as a catalyst deactivator. For example, if hexanoic acid is employed, then a C6 metal ester results while stearic acid may yield a C 16 metal ester.
  • the meta! of the metal ester is a transition metal, Group HA metal, Group IIIA metal, or a combination thereof.
  • compositions may be blended with one or more suitable additional polymers during the production of ethylene/ ⁇ -olefin multiblock interpolymer or subsequently.
  • suitable polymers include, for example, a propylene based plastomer or elastomer, random ethylene copolymers such as AFFINITY® or ENGAGE®, traditional polyethylenes such as HDPE, LLDPE, ULDPE, LDPE and propylene-based polymers such as homopolymer PP, random copolymer PP or PP-based plastomers/elastomers or a combination thereof.
  • the amount of such other polymers differs depending upon the desired properties and compatibility with the specific ethylene/ ⁇ -olefin interpolymer and metal ester employed.
  • Useful propylene based plastomers or elastomers include polypropylenes formed by any means within the skill in the art.
  • the propylene and optional comonomers, such as ethylene or alpha-olefin monomers are polymerized under conditions within the skill in the art, for instance, as disclosed by Galli, et al., Angew. Macromol. Chem., Vol. 120, 73 ( 1984), or by E. P. Moore, et al. in Polypropylene Handbook, Hanser Publishers, New York, 1996, particularly pages 1 1-98.
  • propylene-based polymers include VERSIFYTM polymers (The Dow Chemical Company) and VISTAMAXXTM polymers (ExxonMobil Chemical Co.), LICOCENETM polymers (Clariant), EASTOFLEXTM polymers (Eastman Chemical Co.), REXTACTM polymers (Hunstman), and VESTOPLASTTM polymers (Degussa).
  • Other suitable polymers include propylene- ⁇ -olefins block copolymers and interpolymers, and other propylene based block copolymers and interpolymers known in the art.
  • T m > -6553.3 + 13735(d) - 7051.7(d) 2 ; or (4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ⁇ H in J/g, and a delta quantity, ⁇ T, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ⁇ T and ⁇ H have the following relationships:
  • ⁇ T 48 0 C for ⁇ H greater than 130 J/g , wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 3O 0 C; or
  • (6) a molecular fraction which elutes between 4O 0 C and 130 0 C when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/ ⁇ - olefin interpolymer; or
  • shuttling agent selected from the group consisting of diethylzinc, di(i- butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, i- butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum, i- butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n- octylaluminum di(ethyl(l)
  • a shuttling agent selected from the group consisting of diethylzinc
  • metal of the metal alkyl compound is selected from the group consisting of zinc, aluminum, and gallium.
  • the ionic surfactant comprises a fatty acid salt selected from the group consisting of alkali metal fatty acid salts, alkaline earth metal fatty acid salts, and mixtures thereof.
  • reaction process of one or more of the preceding claims comprising adding a mixture comprising an antioxidant selected from the group consisting of sterically hindered phenols, sterically hindered phenyl phosphites, and mixtures thereof to the product under conditions sufficient to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound.
  • reaction process of one or more of the preceding claims which comprises purging the post-reactor heat exchanger with a gas selected from nitrogen, ethylene, or air.
  • reaction process of one or more of the preceding claims which comprises purging the post-reactor heat exchanger with nitrogen first in one direction and then in the other.
  • a composition comprising an ethylene/ ⁇ -olefin multiblock interpolymer and a metal ester.
  • composition of one or more of the preceding claims wherein the metal of the metal ester is selected from the group consisting of zinc, aluminum, and gallium. 69. The composition of one or more of the preceding claims wherein the metal ester is a metal stearate, a metal octanoate, or a mixture thereof.
  • composition of one or more of the preceding claims wherein the metal ester is present in an anti-fungal effective amount is provided.
  • composition of one or more of the preceding claims wherein the metal ester is present in a nucleating effective amount is provided.
  • composition of one or more of the preceding claims wherein the resulting product has a whiteness index above 50.
  • An automated liquid-handling robot equipped with a heated needle set to 160 0 C is used to add enough 1 ,2,4-trichlorobenzene stabilized with 300 ppm Ionol to each dried polymer sample to give a final concentration of 30 mg/mL.
  • a small glass stir rod is placed into each tube and the samples are heated to 160 0 C for 2 hours on a heated, orbital- shaker rotating at 250 rpm.
  • the concentrated polymer solution is then diluted to 1 mg/ml using the automated liquid-handling robot and the heated needle set to 16O 0 C.
  • a Symyx Rapid GPC system is used to determine the molecular weight data for each sample.
  • a Gilson 350 pump set at 2.0 ml/min flow rate is used to pump helium- purged 1,2-dichlorobenzene stabilized with 300 ppm Ionol as the mobile phase through three Plgel 10 micrometer ( ⁇ m) Mixed B 300mm x 7.5mm columns placed in series and heated to 16O 0 C.
  • a Polymer Labs ELS 1000 Detector is used with the Evaporator set to 250 0 C, the Nebulizer set to 165°C, and the nitrogen flow rate set to 1.8 SLM at a pressure of 60-80 psi (400-600 kPa) N 2 .
  • the polymer samples are heated to 160 0 C and each sample injected into a 250 ⁇ l loop using the liquid-handling robot and a heated needle. Serial analysis of the polymer samples using two switched loops and overlapping injections are used. The sample data is collected and analyzed using Symyx EpochTM software. Peaks are manually integrated and the molecular weight information reported uncorrected against a polystyrene standard calibration curve.
  • Branching distributions are determined by crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain.
  • the samples are dissolved in 1 ,2,4 trichlorobenzene at 160 0 C (0.66 mg/mL) for 1 hr and stabilized at 95 0 C for 45 minutes.
  • the sampling temperatures range from 95 to 30 0 C at a cooling rate of 0.2°C/min.
  • An infrared detector is used to measure the polymer solution concentrations.
  • the cumulative soluble concentration is measured as the polymer crystallizes while the temperature is decreased.
  • the analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.
  • the CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF Software (Version 200 l .b, PolymerChar, Valencia, Spain).
  • the CRYSTAF peak finding routine identifies a peak temperature as a maximum in the dW/dT curve and the area between the largest positive inflections on either side of the identified peak in the derivative curve.
  • the preferred processing parameters are with a temperature limit of 70 0 C and with smoothing parameters above the temperature limit of 0.1, and below the temperature limit of 0.3.
  • the sample is then cooled to - 4O 0 C at 10°C/min cooling rate and held at -40 0 C for 3 minutes.
  • the sample is then heated to 150 0 C at 10°C/min. heating rate. The cooling and second heating curves are recorded.
  • the DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30 0 C and end of melting.
  • the heat of fusion is measured as the area under the melting curve between -30 0 C and the end of melting using a linear baseline.
  • the gel permeation chromatographic system consists of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument.
  • the column and carousel compartments are operated at 140 0 C.
  • Three Polymer Laboratories 10- micron Mixed-B columns are used.
  • the solvent is 1 ,2,4 trichlorobenzene.
  • the samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydro xytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160 0 C.
  • the injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.
  • Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights.
  • the standards are purchased from Polymer Laboratories (Shropshire, UK).
  • the polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000.
  • the polystyrene standards are dissolved at 8O 0 C with gentle agitation for 30 minutes.
  • the narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation.
  • Compression set is measured according to ASTM D 395.
  • the sample is prepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and 0.25 mm thickness until a total thickness of 12.7 mm is reached.
  • the discs are cut from 12.7 cm x 12.7 cm compression molded plaques molded with a hot press under the following conditions: zero pressure for 3 min at 190 0 C, followed by 86 MPa for 2 min at 190 0 C, followed by cooling inside the press with cold running water at 86 MPa.
  • Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
  • Flexural/Secant Modulus/ Storage Modulus Samples are compression molded using ASTM D 1928. Flexural and 2 percent secant moduli are measured according to ASTM D-790. Storage modulus is measured according to ASTM D 5026-01 or equivalent technique.
  • Model #4095-4PR1001 R The pellets are placed between polytetrafluoroethylene sheets, heated at 190 0 C at 55 psi (380 kPa) for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min. The film is then cooled in the press with running cold water at 1.3 MPa for 1 min.
  • the compression molded films are used for optical measurements, tensile behavior, recovery, and stress relaxation.
  • Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D 1746.
  • Procedure A Mineral oil is applied to the film surface to remove surface scratches.
  • Lo is the load at 50% strain at 0 time and Li? is the load at 50 percent strain after 12 hours.
  • DMA Dynamic Mechanical Analysis
  • a 1.5mm plaque is pressed and cut in a bar of dimensions 32xl2mm.
  • the sample is clamped at both ends between fixtures separated by 10mm (grip separation ⁇ L) and subjected to successive temperature steps from -100 0 C to 200 0 C (5°C per step).
  • the torsion modulus G' is measured at an angular frequency of 10 rad/s, the strain amplitude being maintained between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in the linear regime.
  • Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in U.S. Patent No. 4,798,081 and Wilde, L.; RyIe, T.R.; Knobeloch, D.C.; Peat, I. R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. ScL, 20, 441-455 ( 1982), which are incorporated by reference herein in their entirety.
  • the composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20 0 C at a cooling rate of O. rC/min.
  • the column is equipped with an infrared detector.
  • An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120 0 C at a rate of 1.5°C/min.
  • the samples are prepared by adding approximately 3g of a 50/50 mixture of tetrachloroethane-d 2 /orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube.
  • the samples are dissolved and homogenized by heating the tube and its contents to 15O 0 C.
  • the data are collected using a JEOL EclipseTM 400MHz spectrometer or a Varian Unity PlusTM 400MHz spectrometer, corresponding to a 13 C resonance frequency of 100.5 MHz.
  • the data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together.
  • the spectral width is 25,000 Hz with a minimum file size of 32K data points.
  • the samples are analyzed at 130 0 C in a 10 mm broad band probe.
  • the comonomer incorporation is determined using Randall's triad method (Randall, J. C; JMS-Rev. Macromol. Chem. Phys., C29, 201 -317 ( 1989), which is incorporated by reference herein in its entirety.
  • TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB)by stirring for 4 hours at 160 0 C.
  • the polymer solution is forced by 15 psig (100 kPa) nitrogen onto a 3 inch by 4 foot (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 ⁇ m) spherical, technical quality glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801 ) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets, Inc. 63 Industrial Drive, North Tonawanda, NY, 14120).
  • the column is immersed in a thermally controlled oil jacket, set initially to 160 0 C.
  • the column is first cooled ballistically to 125 0 C, then slow cooled to 20 0 C at 0.04 0 C per minute and held for one hour.
  • Fresh TCB is introduced at about 65 ml/min while the temperature is increased at 0.167 0 C per minute.
  • Melt Strength is measured by using a capillary rheometer fitted with a 2.1 mm diameter, 20: 1 die with an entrance angle of approximately 45 degrees. After equilibrating the samples at 190 0 C for 10 minutes, the piston is run at a speed of 1 inch/minute (2.54 cm/minute). The standard test temperature is 190 0 C. The sample is drawn uniaxially to a set of accelerating nips located 100 mm below the die with an acceleration of 2.4 mm/sec 2 . The required tensile force is recorded as a function of the take-up speed of the nip rolls. The maximum tensile force attained during the test is defined as the melt strength. In the case of polymer melt exhibiting draw resonance, the tensile force before the onset of draw resonance was taken as melt strength. The melt strength is recorded in centiNewtons ("cN").
  • MMAO refers to modified methylalumoxane, a triisobutylaluminum modified methylalumoxane available commercially from Akzo-Noble Corporation.
  • Cocatalyst 1 A mixture of methyldi(C
  • shuttling agents employed include diethylzinc (DEZ, SA l ), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum (TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6), i-butylaluminum bis(dimethyl(t- butyl)siloxane) (SA7), i-butylaluminum bis(di(trimethylsilyl)amide) (SA8), n-octylaluminum di(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA l O), i-butylaluminum bis(di(n-pentyl)amide) (SA l 1), n-octylaluminum bis(2,6-d
  • Polymerizations are conducted using a high throughput, parallel polymerization reactor (PPR) available from Symyx Technologies, Inc. and operated substantially according to US Patents No. 6,248,540, 6,030,917, 6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations are conducted at 130 0 C and 200 psi ( 1.4 MPa) with ethylene on demand using 1.2 equivalents of cocatalyst 1 based on total catalyst used ( 1.1 equivalents when MMAO is present). A series of polymerizations are conducted in a parallel pressure reactor (PPR) contained of 48 individual reactor cells in a 6 x 8 array that are fitted with a pre-weighed glass tube.
  • PPR parallel pressure reactor
  • each reactor cell is 6000 ⁇ L.
  • Each cell is temperature and pressure controlled with stirring provided by individual stirring paddles.
  • the monomer gas and quench gas are plumbed directly into the PPR unit and controlled by automatic valves.
  • Liquid reagents are robotically added to each reactor cell by syringes and the reservoir solvent is mixed alkanes.
  • the order of addition is mixed alkanes solvent (4 ml), ethylene, 1 -octene comonomer ( 1 ml), cocatalyst 1 or cocatalyst 1 /MMAO mixture, shuttling agent, and catalyst or catalyst mixture.
  • Examples 1 -4 demonstrate the synthesis of linear block copolymers by the present invention as evidenced by the formation of a very narrow MWD, essentially monomodal copolymer when DEZ is present and a bimodal, broad molecular weight distribution product (a mixture of separately produced polymers) in the absence of DEZ. Due to the fact that Catalyst (Al) is known to incorporate more octene than Catalyst (Bl), the different blocks or segments of the resulting copolymers of the invention are distinguishable based on branching or density.
  • the polymers produced according to the invention have a relatively narrow polydispersity (Mw/Mn) and larger block-copolymer content (trimer, tetramer, or larger) than polymers prepared in the absence of the shuttling agent.
  • the DSC curve for the polymer of example 2 shows a peak with a 109.7 0 C melting point (Tm) with a heat of fusion of 214.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 46.2°C with a peak area of 57.0 percent.
  • the difference between the DSC Tm and the Tcrystaf is 63.5°C.
  • the DSC curve for the polymer of example 3 shows a peak with a 120.7 0 C melting point (Tm) with a heat of fusion of 160.1 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 66.1 0 C with a peak area of 71.8 percent.
  • the difference between the DSC Tm and the Tcrystaf is 54.6°C.
  • the DSC curve for the polymer of example 4 shows a peak with a 104.5 0 C melting point (Tm) with a heat of fusion of 170.7 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 30 0 C with a peak area of 18.2 percent.
  • the difference between the DSC Tm and the Tcrystaf is 74.5°C.
  • the DSC curve for comparative A shows a 90.0 0 C melting point (Tm) with a heat of fusion of 86.7 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 48.5°C with a peak area of 29.4 percent. Both of these values are consistent with a resin that is low in density.
  • the difference between the DSC Tm and the Tcrystaf is 41.8°C.
  • the DSC curve for comparative B shows a 129.8°C melting point (Tm) with a heat of fusion of 237.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 82.4 0 C with a peak area of 83.7 percent. Both of these values are consistent with a resin that is high in density.
  • the difference between the DSC Tm and the Tcrystaf is 47.4 0 C.
  • the DSC curve for comparative C shows a 125.3 0 C melting point (Tm) with a heat of fusion of 143.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 81.8 0 C with a peak area of 34.7 percent as well as a lower crystalline peak at 52.4 0 C.
  • the separation between the two peaks is consistent with the presence of a high crystalline and a low crystalline polymer.
  • the difference between the DSC Tm and the Tcrystaf is 43.5 0 C.
  • the remaining solvent is combined with 1 -octene, ethylene, and hydrogen (where used) and fed to the reactor.
  • a mass flow controller is used to deliver hydrogen to the reactor as needed.
  • the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
  • the catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor.
  • the reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated.
  • Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer.
  • the product stream is then heated by passing through a heat exchanger before devolatilization.
  • the polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.
  • Process details and results are contained in Table 2. Selected polymer properties are provided in Table 3. Table 2 Process details for preparation of exemplary polymers
  • the DSC curve for the polymer of example 5 shows a peak with a 1 19.6 0 C melting point (Tm) with a heat of fusion of 60.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 47.6 0 C with a peak area of 59.5 percent.
  • the delta between the DSC Tm and the Tcrystaf is 72.O 0 C.
  • the DSC curve for the polymer of example 6 shows a peak with a 1 15.2 0 C melting point (Tm) with a heat of fusion of 60.4 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 44.2 0 C with a peak area of 62.7 percent.
  • the delta between the DSC Tm and the Tcrystaf is 71.0 0 C.
  • the DSC curve for the polymer of example 7 shows a peak with a 121.3 0 C melting point with a heat of fusion of 69.1 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 49.2°C with a peak area of 29.4 percent.
  • the delta between the DSC Tm and the Tcrystaf is 72.1°C.
  • the DSC curve for the polymer of example 8 shows a peak with a 123.5 0 C melting point (Tm) with a heat of fusion of 67.9 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 80.1 0 C with a peak area of 12.7 percent.
  • the delta between the DSC Tm and the Tcrystaf is 43.4 0 C.
  • the DSC curve for the polymer of example 9 shows a peak with a 124.6 0 C melting point (Tm) with a heat of fusion of 73.5 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 80.8 0 C with a peak area of 16.0 percent.
  • the delta between the DSC Tm and the Tcrystaf is 43.8 0 C.
  • the DSC curve for the polymer of example 10 shows a peak with a 1 15.6 0 C melting point (Tm) with a heat of fusion of 60.7 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 40.9 0 C with a peak area of 52.4 percent.
  • the delta between the DSC Tm and the Tcrystaf is 74.7°C.
  • the DSC curve for the polymer of example 1 1 shows a peak with a 1 13.6 0 C melting point (Tm) with a heat of fusion of 70.4 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 39.6 0 C with a peak area of 25.2 percent.
  • the delta between the DSC Tm and the Tcrystaf is 74.1 0 C.
  • the DSC curve for the polymer of example 12 shows a peak with a 1 13.2 0 C melting point (Tm) with a heat of fusion of 48.9 J/g.
  • Tm melting point
  • the corresponding CRYSTAF curve shows no peak equal to or above 30 0 C. (Tcrystaf for purposes of further calculation is therefore set at 30 0 C).
  • the delta between the DSC Tm and the Tcrystaf is 83.2°C.
  • the DSC curve for the polymer of example 13 shows a peak with a 1 14.4 0 C melting point (Tm) with a heat of fusion of 49.4 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 33.8 0 C with a peak area of 7.7 percent.
  • the DSC for the polymer of example 14 shows a peak with a 120.8 0 C melting point (Tm) with a heat of fusion of 127.9 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 72.9 0 C with a peak area of 92.2 percent.
  • the delta between the DSC Tm and the Tcrystaf is 47.9 0 C.
  • the DSC curve for the polymer of example 15 shows a peak with a 1 14.3 0 C melting point (Tm) with a heat of fusion of 36.2 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 32.3 0 C with a peak area of 9.8 percent.
  • the delta between the DSC Tm and the Tcrystaf is 82.O 0 C.
  • the DSC curve for the polymer of example 16 shows a peak with a 1 16.6 0 C melting point (Tm) with a heat of fusion of 44.9 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 48.0 0 C with a peak area of 65.0 percent.
  • the delta between the DSC Tm and the Tcrystaf is 68.6 0 C.
  • the DSC curve for the polymer of example 17 shows a peak with a 1 16.0 0 C melting point (Tm) with a heat of fusion of 47.0 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 43.1 0 C with a peak area of 56.8 percent.
  • the delta between the DSC Tm and the Tcrystaf is 72.9°C.
  • the DSC curve for the polymer of example 18 shows a peak with a 120.5 0 C melting point (Tm) with a heat of fusion of 141.8 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 70.0 0 C with a peak area of 94.0 percent.
  • the delta between the DSC Tm and the Tcrystaf is 50.5 0 C.
  • the DSC curve for the polymer of example 19 shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 174.8 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 79.9 0 C with a peak area of 87.9 percent.
  • the delta between the DSC Tm and the Tcrystaf is 45.0 0 C.
  • the DSC curve for the polymer of comparative D shows a peak with a 37.3 0 C melting point (Tm) with a heat of fusion of 31.6 J/g.
  • the corresponding CRYSTAF curve shows no peak equal to and above 30 0 C. Both of these values are consistent with a resin that is low in density.
  • the delta between the DSC Tm and the Tcrystaf is 7.3°C.
  • the DSC curve for the polymer of comparative E shows a peak with a 124.0 0 C melting point (Tm) with a heat of fusion of 179.3 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 79.3°C with a peak area of 94.6 percent. Both of these values are consistent with a resin that is high in density.
  • the delta between the DSC Tm and the Tcrystaf is 44.6°C.
  • the DSC curve for the polymer of comparative F shows a peak with a 124.8 0 C melting point (Tm) with a heat of fusion of 90.4 J/g.
  • the corresponding CRYSTAF curve shows the tallest peak at 77.6°C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of both a high crystalline and a low crystalline polymer.
  • the delta between the DSC Tm and the Tcrystaf is 47.2 0 C.
  • Comparative G* is a substantially linear ethylene/ 1-octene copolymer (AFFINITY®, available from The Dow Chemical Company)
  • Comparative H* is an elastomeric, substantially linear ethylene/ 1-octene copolymer (AFFINITY®EG8100, available from The Dow Chemical Company)
  • Comparative I is a substantially linear ethylene/1 -octene copolymer (AFF1NITY®PL184O, available from The Dow Chemical Company)
  • Comparative J is a hydrogenated styrene/butadiene/styrene triblock copolymer (KRATONTM G 1652, available from KRATON Polymers)
  • Comparative K is a thermoplastic vulcanizate (TPV, a poly(ethylene/ 1-octene copolymer (AFFINITY®, available from The Dow Chemical Company)
  • Comparative H* is an elastomeric, substantially linear ethylene/ 1-octene copolymer (AFFINITY®EG8100, available from
  • Comparative F (which is a physical blend of the two polymers resulting from simultaneous polymerizations using catalyst A l and Bl ) has a 1 mm penetration temperature of about 70 0 C, while Examples 5-9 have a 1 mm penetration temperature of 100 0 C or greater. Further, examples 10-19 all have a 1 mm penetration temperature of greater than 85°C, with most having 1 mm TMA temperature of greater than 9O 0 C or even greater than 100 0 C. This shows that the novel polymers have better dimensional stability at higher temperatures compared to a physical blend.
  • Comparative J (a commercial SEBS) has a good 1 mm TMA temperature of about 107 0 C, but it has very poor (high temperature 70 0 C) compression set of about 100 percent and it also failed to recover (sample broke) during a high temperature (80 0 C) 300 percent strain recovery.
  • the exemplified polymers have a unique combination of properties unavailable even in some commercially available, high performance thermoplastic elastomers.
  • Table 4 shows a low (good) storage modulus ratio, G'(25°C)/G'(100°C), for the inventive polymers of 6 or less, whereas a physical blend
  • Comparative F has a storage modulus ratio of 9 and a random ethylene/octene copolymer (Comparative G) of similar density has a storage modulus ratio an order of magnitude greater (89). It is desirable that the storage modulus ratio of a polymer be as close to 1 as possible. Such polymers will be relatively unaffected by temperature, and fabricated articles made from such polymers can be usefully employed over a broad temperature range. This feature of low storage modulus ratio and temperature independence is particularly useful in elastomer applications such as in pressure sensitive adhesive formulations.
  • Example 5 has a pellet blocking strength of 0 MPa, meaning it is free flowing under the conditions tested, compared to
  • Comparatives F and G which show considerable blocking. Blocking strength is important since bulk shipment of polymers having large blocking strengths can result in product clumping or sticking together upon storage or shipping, resulting in poor handling properties.
  • High temperature (70 0 C) compression set for the inventive polymers is generally good, meaning generally less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent.
  • Comparatives F, G, H and J all have a 70 0 C compression set of 100 percent (the maximum possible value, indicating no recovery).
  • Good high temperature compression set (low numerical values) is especially needed for applications such as gaskets, window profiles, o-rings, and the like.
  • Table 5 shows results for mechanical properties for the new polymers as well as for various comparison polymers at ambient temperatures. It may be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a volume loss of less than about 90 mm 3 , preferably less than about 80 mm 3 , and especially less than about 50 mm 3 . In this test, higher numbers indicate higher volume loss and consequently lower abrasion resistance.
  • Tear strength as measured by tensile notched tear strength of the inventive polymers is generally 1000 mJ or higher, as shown in Table 5. Tear strength for the inventive polymers can be as high as 3000 mJ, or even as high as 5000 mJ. Comparative polymers generally have tear strengths no higher than 750 mJ.
  • Table 5 also shows that the polymers of the invention have better retractive stress at 150 percent strain (demonstrated by higher retractive stress values) than some of the comparative samples. Comparative Examples F, G and H have retractive stress value at 150 percent strain of 400 kPa or less, while the inventive polymers have retractive stress values at 150 percent strain of 500 kPa (Ex. 1 1) to as high as about 1 100 kPa (Ex. 17).
  • Polymers having higher than 150 percent retractive stress values would be quite useful for elastic applications, such as elastic fibers and fabrics, especially nonwoven fabrics.
  • Other applications include diaper, hygiene, and medical garment waistband applications, such as tabs and elastic bands.
  • Table 5 also shows that stress relaxation (at 50 percent strain) is also improved (less) for the inventive polymers as compared to, for example, Comparative G.
  • Lower stress relaxation means that the polymer retains its force better in applications such as diapers and other garments where retention of elastic properties over long time periods at body temperatures is desired.
  • optical properties reported in Table 6 are based on compression molded films substantially lacking in orientation. Optical properties of the polymers may be varied over wide ranges, due to variation in crystallite size, resulting from variation in the quantity of chain shuttling agent employed in the polymerization.
  • the ether in the flask is evaporated under vacuum at ambient temperature, and the resulting solids are purged dry with nitrogen. Any residue is transferred to a weighed bottle using successive washes of hexane. The combined hexane washes are then evaporated with another nitrogen purge, and the residue dried under vacuum overnight at 40 0 C. Any remaining ether in the extractor is purged dry with nitrogen.
  • a second clean round bottom flask charged with 350 mL of hexane is then connected to the extractor.
  • the hexane is heated to reflux with stirring and maintained at reflux for 24 hours after hexane is first noticed condensing into the thimble. Heating is then stopped and the flask is allowed to cool. Any hexane remaining in the extractor is transferred back to the flask.
  • the hexane is removed by evaporation under vacuum at ambient temperature, and any residue remaining in the flask is transferred to a weighed bottle using successive hexane washes.
  • the hexane in the flask is evaporated by a nitrogen purge, and the residue is vacuum dried overnight at 40 0 C.
  • Continuous solution polymerizations are carried out in a computer controlled well-mixed reactor.
  • Purified mixed alkanes solvent IsoparTM E available from Exxon Mobil, Inc.
  • ethylene, 1 -octene, and hydrogen are combined and fed to a 27 gallon reactor.
  • the feeds to the reactor are measured by mass-flow controllers.
  • the temperature of the feed stream is controlled by use of a glycol cooled heat exchanger before entering the reactor.
  • the catalyst component solutions are metered using pumps and mass flow meters.
  • the reactor is run liquid-full at approximately 550 psig pressure.
  • water and additive are injected in the polymer solution.
  • the water hydrolyzes the catalysts, and terminates the polymerization reactions.
  • the post reactor solution is then heated in preparation for a two-stage devolatization.
  • the solvent and unreacted monomers are removed during the devolatization process.
  • the polymer melt is pumped to a die for underwater pellet cutting.
  • Continuous solution polymerizations are carried out in a computer controlled autoclave reactor equipped with an internal stirrer.
  • Purified mixed alkanes solvent IsoparTM E available from ExxonMobil Chemical Company
  • ethylene at 2.70 lbs/hour (1.22 kg/hour) 1-octene, and hydrogen (where used) are supplied to a 3.8 L reactor equipped with a jacket for temperature control and an internal thermocouple.
  • the solvent feed to the reactor is measured by a mass-flow controller.
  • a variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst and cocatalyst injection lines and the reactor agitator.
  • the remaining solvent is combined with 1 -octene, ethylene, and hydrogen (where used) and fed to the reactor.
  • a mass flow controller is used to deliver hydrogen to the reactor as needed.
  • the temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor.
  • the catalyst component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor.
  • the reactor is run liquid-full at 500 psig (3.45 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. All exit lines from the reactor are steam traced and insulated.
  • Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives and passing the mixture through a static mixer.
  • the product stream is then heated by passing through a heat exchanger before devolatilization.
  • the polymer product is recovered by extrusion using a devolatilizing extruder and water cooled pelletizer.
  • Irganox 1010 is Tetrakismethylene(3,5-di-t-butyl-4- hydroxyhydrocinnamate)methane.
  • Irganox 1076 is Octadecyl-3-(3',5'-di-t-butyl-4'- hydroxyphenyl)propionate.
  • Irgafos 168 is Tris(2,4-di-t-butylphenyl)phosphite.
  • Chimasorb 2020 is 1 ,6-Hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)- polymer with 2,3,6-trichloro-l,3,5-triazine, reaction products with, N-butyl-1- butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.
  • Example 22 Improving the ethylene/ ⁇ -olefin multiblock interpolymer process of Examples 1-21
  • Each of the above Examples 1-21 to produce ethylene/ ⁇ -olefin multiblock interpolymer may be repeated and a metal alkyl compound may be reacted with an acid to produce a soluble metal ester; or an ionic surfactant may be added to the reactor or reactor effluent after the reaction; or a mixture comprising an antioxidant may be added to the product under conditions sufficient to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound; or the post-reactor heat exchanger may be purged with an inert gas under conditions to remove metal oxide from the post-reactor heat exchanger.
  • Ethylene/ ⁇ -olefin multiblock interpolymer having a melt index of 15 and a density of 0.877 g/cc is produced in a similar manner to that Example 19.
  • Water is employed as a catalyst deactivator at a 1.5: 1 molar ratio with respect to the diethyl zinc chain shuttling agent.
  • 500 ppm of calcium stearate (on a polymer basis) is added to the polymer stream just prior to the post-reactor heat exchanger (PRH).
  • PRH post-reactor heat exchanger
  • the heat transfer efficiency is measured by calculating a dimensionless U value based on the flows and temperatures of the polymer stream and the heat transfer fluid.
  • the heat transfer efficiency drop is less than about 1% per day whereas continuously producing the same product in the absence of calcium stearate addition causes the heat transfer efficiency to drop approximately 5% per day.
  • the amount of fouling is dependent upon the amount of calcium stearate employed as shown in the table below.
  • the addition of calcium stearate at levels of approximately from about 2 to about 3 times as high as the amount of Zn in the polymer (on a mass basis) leads to post reactor heater fouling at a rate approximately 1/1 Oth that of identical runs performed without the addition of calcium stearate. Effect of calcium stearate and zinc on ost reactor heater foulin
  • Ethylene/ ⁇ -olefin multiblock interpolymer is produced in a similar manner as in Example 23 except that water was not employed as the catalyst deactivator and calcium stearate is not added. Instead, octanoic acid is mixed with Isopar E at room temperature and then pumped into the approximately 17% polymer stream which is at approximately 140 0 C and located prior to the PRH. The amount of octanoic acid employed is 2 moles of acid for every mole of zinc in the process stream. The efficiency of the PRH drops less than 0.1% per day over a six day period as compared to an approximately 5% drop per day without the use of octanoic acid.
  • Ethylene/ ⁇ -olefin multiblock interpolymer is produced in a similar manner as in Example 24 except that stearic acid is employed instead of octanoic acid.
  • the efficiency of the PRH drops less than 0.1% per day over a four day period as compared to an approximately 5% drop per day without the use of stearic acid.
  • Ethylene/ ⁇ -olefin multiblock interpolymer is produced in a similar manner to that in examples 1-21 except that various additives are added and the amount and temperature of water is varied during the catalyst neutralization step as shown in the table below.
  • the amount of zinc in each final product is approximately 240 ppm as calculated by mass balance. It is determined that when necessary to increase the water solubility, a small amount of an alcohol is useful to break surface tension. Similarly, increasing the water temperature yields an increase in solubility.
  • whiteness index increases (gray color formation is mitigated) by adding antioxidants during the catalyst neutralization step, adding hot (>50C) water temperature during the catalyst neutralization step, and/or adding an alcohol (e.g. isopropanol) during the catalyst neutralization step. That is if one consider the third row as the control a whiteness index of 33 is obtained. When an antioxidant is added before the PRH as in rows 1 , 2, 7 and 8 the whiteness index increases.
  • Example 27 Adding a Mixture Comprising Water and Stearic Acid
  • Ethylene/a-olefin multiblock interpolymer is produced in a similar manner as in Example 23 except that a mixture of water and stearic acid are employed as the catalyst deactivator and calcium stearate is not added. Instead, stearic acid is mixed with Isopar E at room temperature and then pumped into the approximately 17% polymer stream which is at approximately 140 0 C along with the water and located prior to the PRH.
  • the amount of octanoic acid employed is 1 mole of acid for every mole of zinc in the process stream and the amount of water employed is 0.75 moles of water for every mol of Zinc in the process stream.
  • the efficiency of the PRH can be expected to drop less than 0.1% per day over a three day period as compared to an approximately 5% drop per day without the use of water and stearic acid.
  • Ethylene/a-olefin multiblock interpolymer is produced in a similar manner as in Example 23 except that a mixture of water and octanoic acid are employed as the catalyst deactivator and calcium stearate is not added. Instead, octanoic acid is mixed with Isopar E at room temperature and then pumped into the approximately 17% polymer stream which is at approximately 140 0 C along with the water and located prior to the PRH. The amount of octanoic acid employed is 1 mole of acid for every mole of zinc in the process stream and the amount of water employed is 0.75 moles of water for every mol of Zinc in the process stream. The efficiency of the PRH can be expected to drop less than 0.1% per day over a three day period as compared to an approximately 5% drop per day without the use of water and octanoic acid.
  • Ethylene/ ⁇ -olefin multiblock interpolymer is produced in a similar manner to that in Examples 1-21.
  • a solvent is flowed through the post-reactor heat exchanger at approximately 185C to dissolve any remaining polymer.
  • Nitrogen is used to pad all solvent out of the PRH.
  • a filter bag is placed over one outlet of the PRH. Nitrogen is blown through the exchanger in a first direction toward the outlet. The filter bag is removed and a new one installed at the opposite end of the PRH. Nitrogen is blown through the exchanger in the opposite direction. Prior to the nitrogen purge the heat transfer efficiency of the PRH is less than 65% of the value for a completely clean exchanger while after the nitrogen purge the heat transfer efficiency of the PRH is greater than 90% of the value for a clean exchanger.
  • a post reactor shell and tube heat exchanger heat exchanger comprising 19 tubes is employed to produce a LLDPE (1 MI, 0.920 g/cc) in Isopar E at 23% polymer concentration.
  • the pressure is reduced at the inlet pressure such that the ⁇ P (psi) (inlet pressure-outlet pressure) varies as shown below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Selon l'invention, des procédés de réaction améliorés consistent à faire réagir un mélange pour former un produit contenant un alkyle métallique, un oxyde métallique ou un mélange correspondant et, puis, à acheminer ledit produit jusqu'à un échangeur thermique de post-réaction. L'amélioration comprend une ou plusieurs étapes suivantes qui consistent à (1) faire réagir un composé d'alkyle métallique avec un acide pour produire un ester métallique soluble ou à (2) ajouter un tensioactif ionique, ou à (3) ajouter au produit un mélange contenant un antioxydant dans des conditions permettant d'éviter la formation de quantités importantes de métal insoluble ou de composés métalliques provenant du composé d'alkyle métallique, ou à (4) purger l'échangeur thermique de post-réaction avec un gaz inerte dans certaines conditions afin d'éliminer l'oxyde métallique provenant de l'échangeur thermique de post-réaction.
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CN102124050A (zh) 2011-07-13
US20150112005A1 (en) 2015-04-23
US8933156B2 (en) 2015-01-13
ES2959468T3 (es) 2024-02-26
US9932425B2 (en) 2018-04-03
CN102124050B (zh) 2013-06-12
US20110086963A1 (en) 2011-04-14
AR072672A1 (es) 2010-09-15
WO2009155155A1 (fr) 2009-12-23
BRPI0909923A2 (pt) 2019-03-06

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